MOLCHANOV et al.
84
CH, J = 6 Hz), 7.01 d (1H, C6H3, J = 8 Hz), 7.22 d.d (1H,
C6H3, J = 8, 2 Hz), 7.40 d (1H, C6H3, J = 2 Hz). Found,
%: 49.10; H 3.82; N 12.10. C14H13Cl2N3O3. Calculated,
%: C 49.14; H 3.83; N 12.28.
1.39 t (1H, CH2, J = 6 Hz), 2.01 d.d (1H, CH2, J = 6,
1.5 Hz), 2.93 s (2H, CH2), 3.48 d.d (1H, CH, J = 6,
1.5 Hz), 7.00 d (1H, C6H3, J = 8 Hz), 7.167.28 m (1H,
C6H3), 7.39 d.d (1H, C6H3, J = 8, 2 Hz); XVIIIb: 1.75 t
(1H, CH2, J = 7 Hz), 2.13 d.d (1H, CH2, J = 7, 2.5 Hz),
2.86 d (1H, CH2, J = 19 Hz), 3.23 d (1H, CH2, J =
19 Hz), 3.73 d.d (1H, CH, J = 7, 2.5 Hz), 7.00 d (1H,
C6H3, J = 8 Hz), 7.167.28 m (1H, C6H3), 7.39 d.d
(1H, C6H3, J = 8, 2 Hz). Found, %: C 53.40; H 4.12;
N 4.27. C14H13Cl2NO3. Calculated, %: C 53.52; H 4.17;
N 4.46.
3-Chloro-7-(4-fluorophenyl)-1,2,7-triazaspiro-
[4.4]non-1-ene-6,8-dione (XVId) was synthesized
from 0.30 g (1.0 mmol) of compound IVf. Yield 0.25 g
1
(89%), mp 118120°C (decomp.). H NMR spectrum
(CDCl3), d, ppm: 1.94 d.d (1H, CH2, J = 14, 6 Hz),
3.01 d.d (1H, CH2, J = 14, 6 Hz), 3.10 d (1H, CH2, J =
19 Hz), 3.60 d (1H, CH2, J = 19 Hz), 6.43 t (1H, CH, J =
6 Hz), 7.197.36 m (4H, C6H4). Found, %: C 51.06;
H 3.16; N 14.79. C12H9ClFN3O2. Calculated, %: C 51.17;
H 3.22; N 14.92.
1,1-Dibromo-5-(4-chlorophenyl)-5-azaspiro-
[2.4]heptane-4,6-dione (XIXa). A mixture of 0.40 g
(1.5 mmol) of compound IVd and 0.1 ml of bromine in
6 ml of glacial acetic acid was heated for 2 h at 70°C.
The solvent was distilled off under reduced pressure, the
residue was dissolved in diethyl ether, and the solution
was washed with a solution of sodium sulfite, dried over
MgSO4, and evaporated. The residue was subjected to
column chromatography on silica gel using hexaneethyl
acetate (2:1, by volume) as eluent. Yield 0.13 g (22%),
7-(4-Bromophenyl)-3-chloro-1,2,7-triazaspiro-
[4.4]non-1-ene-6,8-dione (XVIe) was synthesized
from 0.30 g (0.97 mmol) of compound IVe. Yield 0.27 g
1
(83%), mp 121123°C (decomp.). IR spectrum, n, cm :
1030, 1090, 1250, 1390, 1400, 1510, 1720 v.s, 3050.
1H NMR spectrum (CDCl3), d, ppm: 1.92 d.d (1H, CH2,
J = 14, 6 Hz), 2.99 d.d (1H, CH2, J = 14, 6 Hz), 3.10 d
(1H, CH2, J = 19 Hz), 3.57 d (1H, CH2, J = 19 Hz), 6.42 t
(1H, CH, J = 6 Hz), 7.19 d (2H, C6H4, J = 8 Hz), 7.65 d
(2H, C6H4, J = 8 Hz). Found, %: C 41.98; H 2.69;
N 12.14. C12H9BrClN3O2. Calculated, %: C 42.07;
H 2.65; N 12.27.
1
mp 156158°C. IR spectrum, n, cm : 1020, 1040, 1090,
1160, 1380 s, 1490, 1720 v.s, 3050. 1H NMR spectrum
(CDCl3), d, ppm: 2.15 d (1H, CH2, J = 8 Hz), 2.67 d (1H,
CH2, J = 8 Hz), 3.01 d (1H, CH2, J = 19 Hz), 3.48 d (1H,
CH2, J = 19 Hz), 7.35 d (2H, C6H4, J = 8 Hz), 7.48 d
(2H, C6H4, J = 8 Hz). 13C NMR spectrum, dC, ppm: 27.6
(C3); 33.5 (C1); 34.8 (C2); 38.4 (C7); 127.9, 129.8, 130.6,
135.1 (Carom); 171.9, 172.8 (CO). Found, %: C 36.58;
H 2.13; N 3.28. C12H8Br2ClNO2. Calculated, %: C 36.63;
H 2.05; N 3.56.
1-Chloro-5-phenyl-5-azaspiro[2.4]heptane-4,6-
dione (XVIIa/XVIIIa). Compound XVIa, 0.20 g
(0.76 mmol), was heated for 5 min at 140°C under
reduced pressure (20 mm). The resulting material was
cooled and recrystallized from ethanol. Yield of
XVIIa/XVIIIa (isomer mixture) 0.11 g (61%). 1H NMR
spectrum (CDCl3), d, ppm: XVIIa: 1.37 t (1H, CH2, J =
6 Hz), 1.99 d.d (1H, CH2, J = 6, 1.5 Hz), 2.90 s (2H,
CH2), 3.45 d.d (1H, CH, J = 6, 1.5 Hz), 7.227.48 m
(5H, C6H5); XVIIIa: 1.73 t (1H, CH2, J = 7 Hz), 2.11 d.d
(1H, CH2, J = 7, 2.5 Hz), 2.86 d (1H, CH2, J = 19 Hz),
3.22 d (1H, CH2, J = 19 Hz), 3.71 d.d (1H, CH, J = 7,
2.5 Hz), 7.227.48 m (5H, C6H5). Found, %: C 61.20;
H 4.22; N 5.77. C12H10ClNO2. Calculated, %: C 61.16;
H 4.28; N 5.94.
1,1-Dibromo-1-chloro-5-(3-chloro-4-methyl-
phenyl)-5-azaspiro[2.4]heptane-4,6-dione (XIXb)
was synthesized as described above for compound XIXa
from 0.40 g (1.4 mmol) of IVc. Yield 0.09 g (16%),
1
mp 173175°C. IR spectrum (CHCl3), n, cm : 1020,
1040, 1090, 1170, 1380 s, 1490, 1720 v.s, 3050. 1H NMR
spectrum (CDCl3), d, ppm: 2.15 d (1H, CH2, J = 8 Hz),
2.38 s (3H, CH3), 2.68 d (1H, CH2, J = 8 Hz), 3.03 d
(1H, CH2, J = 19 Hz), 3.50 d (1H, CH2, J = 19 Hz),
7.187.43 m (3H, C6H3). Found, %: C 38.28; H 2.34;
N 3.18. C13H10Br2ClNO2. Calculated, %: C 38.32;
H 2.47; N 3.44.
1-Chloro-5-(3-chloro-4-ethoxyphenyl)-5-aza-
spiro[2.4]heptane-4,6-dione (XVIIb/XVIIIb).
Compound XVIc, 0.20 g (0.58 mmol), was heated for 5
min at 130°C under reduced pressure (20 mm). The
resulting material was cooled and recrystallized from
ethanol. Yield of XVIIb/XVIIIb (isomer mixture) 0.13 g
1,1-Dibromo-1-chloro-5-(4-fluorophenyl)-5-aza-
spiro[2.4]heptane-4,6-dione (XIXc) was synthesized
as described above for compound XIXa from 0.40 g
(1.6 mmol) of IVf. Yield 0.074 g (19%), mp 187188°C.
1H NMR spectrum (CDCl3), d, ppm: 2.17 d (1H, CH2,
J = 8 Hz), 2.70 d (1H, CH2, J = 8 Hz), 3.05 d (1H, CH2,
1
(72%). H NMR spectrum (CDCl3), d, ppm: XVIIb:
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005